Textile-finishing composition, method of treating wool-containing textile material therewith and product thereof



Patented July 4, 1950 TEXTILE-FINISHING COMPOSITION, METH- OD OF TREATING WOOL-CONTAINING TEXTILE MATERIAL THEREWITH AND PRODUCT THEREOF Roy H. Kienle and Chester A. Amick, Bound Brook, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine N Drawing. Application March 5, 1948. Serial No. 13,348

17 Claims. 1

This invention relates broadly to new and useful textile-finishing compositions, to the treatment of wool-containing textile materials therewith and to the products of such treatment. The invention is especially concerned with the finishing of woolen textiles, e. g., woolen yarns and cloth or fabric, raw wool and the like, as well as wool-containing textiles in which the wool is blended with other fibers, e. g., cellulosic fibers including cotton fibers.

The embodiment of our invention which is directed to a textile-treating or Ainishing composition or agent is concerned with such a treating material which comprises an intimate and homogeneous association of ingredients comprising (1) an alkylated methylol melamine which is at least partly soluble and preferably substantially completely soluble in water, e. g., a water-soluble methylated methylol melamine, more particularly a water-soluble methylated polymethylol (dimethylol, trimethylol, etc.) melamine, and (2) at least one compound of the class consisting of melamine fiuosilicates and melamine fiuoborates in a ratio, by weight, corresponding to from 0.05 (about 0.05) to 1 (about 1) part, more particularly from about 0.05 to about 0.8 or about 0.9 part, and specifically from about 0.05 to about 0.5 part, of the compound of (2) for each part of the alkylated methylol melamine of (1). Such textilefinishing agents are especiall adapted for rendering wool-containing textile material, e. g., a woolen .cloth or other fabric, resistant to shrinking and to attack by moths and other insects. The wool-containing textile is impregnated with a combination, as in the form of an aqueous liquid composition comprising the aforesaid alkylated methylol melamine and melamine fiuosilicate or fluoborate, or mixture thereof in any proportion,-the melamine salt or salts being present in the combination or homogeneous association with the alkylated methylol melamine in weight ratios such as previously have been stated.

After the textile material has been impregnated, and preferably homogeneously impregnated, with the aforementioned ingredients, which, depending upon their water-solubilities and concentrations, can be applied either in dissolved or dispersed state, the alkylated methylol melamine is cured in situ in intimate contact with the melamine salt to a water-soluble (substantially water-insoluble) state, yielding an impregnant which is resistant to laundering, that is, it is washfast (substantially washfast). The total amountof the alkylated methylol melamine plus the melamine salt or salts which is applied to the textile material is such that the finished textile contains from 2% (about 2%) to 25% (about 25%), more particularly from 4 to 20 or 25% (about 4 to about 20 or 25%), by weight of the dry textile, of an impregnant comprising cured alkylated methylol melamine, specifically cured methylated methylol melamine, in combination (more particularly in the form of a homogeneous association) with a melamine fluosilicate or fluoborate or mixture thereof. The scope of the invention also includes the products resulting from the treatment of wool-containing textile materials with textilefinishing compositions or agents of the kind briefly described above.

It has been the practice for many years to apply mothproofing or insecticidal materials to woolen textiles. Various mothproofing or insecticidal compounds or compositions have been used or suggested for this purpose, including various organic and inorganic fluorides and silicofiuorides. For example, Patent No. 2,340,328- Jones discloses a mothproofing composition containing magnesium silicofiuoride and a lo'wer alkanolamine silicofluoride in particular ratios; Patent No. 2,176,894-Engels et al. discloses a stable mothproofing solution containing triethanolamine silicofiuoride, aluminum sulfate and a sulfated primary alcohol having from 12 to 22 carbon atoms; Patent No. 2,075,359-Sa1zberg et al. discloses an insecticide comprising a fiuosilicate of an organic base, more particularl a mothproofing solution comprising triethanolamine fiuosilicate; and Patent No. 2,163,104Salzberg discloses a fluosilicate of a polymeric amino-nitrogen-com taining substance, which polymer is insoluble in water and in 5% aqueous ammonia but is soluble in 2% aqueous acetic acid and is capable of being formed into a coherent film. Also, in the copending application of George L. Boyer and Chester A. Amick, Serial'No.'610,665, filed August 13, 1945, are disclosed and claimed textile-finishing compositions comprising an aqueous solution containing certain particular proportions of a watersoluble alkylated methylol melamine and a finely divided fluoride of an alkali-forming metal, specifically sodium fluoride, and a method of finishing woolen textiles which involves treating the textile with such a finishing composition. Widmer et al. Patent No. 2,318,121 discloses compositions comprising an aminotriazine-aldehyde condensation product as a binder for fungicidal or insecticidal dusting agents which are to be sprayed upon a surface to be protected.

The present invention has as alprincipal object the provision of novel textile-finishing compositions containing (1) a fiuosilicate or fiuoborate (or mixturethereof) of melamine, which compounds are contact insecticides having substantial water-solubility and also are capable of functioning as stomach poisons, and (2) a curable or potentially curable resinous material which, by physical or chemical means or by both such means, can render the water-soluble insecticide resistant to laundering when the resin itself is cured to a water-insoluble state, and which also can impart resistance to shrinking to a woolcontaining textile undergoing treatment. Another object of the invention is to provide solutions or dispersions of this type in which the resinous binder for the insecticide imparts shrinkage control to the impregnated textile material, whereby the finished textile is rendered resistant, even after repeated launderings, both to the attack of insects and insect larvae (including carpet beetle larvae) and, also, to shrinkage. Still further objects of the invention are the provision of methods of imparting the above properties to woolen or wool-containing textiles by the use of the above-described finishing compositions and the products of such methods.

The foregoing and other objects are attained as briefly described in the second and third paragraphs of this specification and more fully hereafter. We have found that compositions capable oi imparting shrinkage control and insecticidal properties, specifically mothproofing properties, to wool-containing textiles, which properties are retained completely or substantially completely even after repeated launderings, are obtained by dispersing or dissolving a melamine fiuosilicate or fluoborate or a mixture thereof in an aqueous composition containing an alkylated or alcoholreacted methylol melamine, which is at least partly soluble in water and which, preferably, is substantially completely soluble in water, for instance a water-soluble methylated methylol melamine.

The application to woolen textiles of aqueous alkylated methylol melamine solutions or dispersions for the purpose of reducing the felting and shrinking tendencies of the woolen textile is described in Johnstone et al. Reissue Patent No. 22,566, and is now in wide commercial use. The present invention is based on our discovery that when a wool-containing textile material is impregnated with such an alkylated methylol melamine and a melamine salt of an inorganic acid having a fluorine-containing anion of the kind aforementioned, i. e., melamine fiuosilicate or fiuoborate or mixtures thereof, within a particular range of proportions of each, and when the aforementioned combination of impregnants is present in the treated textile in an adequate amount, the impregnated textile material is rendered not only resistant to felting and shrinking but also to attack by insect larvae, specifically carpet beetle larvae, even after repeated launderings. This was quite surprising and unexpected since ordinarily it would be expected that insolubilization of the alkylated methylol melamine by curing would mask the ability of the melamine iluosilicate or fluoborate to function as an insecticide; also, it normally would be expected that the added melamine salt, which by itself is not able to impart shrink-resistant characteristics to wool-containing textile material, would adversely affect the ability of the alkylated methylol melamine to reduce the felting and shrinking tedencies of such a textile. Contrary to expecta- 4 tions the alkylated methylol melamine and the melamine salt coact upon application to woolen textiles, and the like, of an aqueous solution of the alkylated methylol melamine having the melamine salt dissolved or dispersed therein, followed by heating the impregnated textile to insolubilize the resin therein.

The substantially completely water-soluble alkylated, specifically methylated, methylol melamines provide optimum results in carrying our invention into eflect, and therefore are preferred. They may be prepared as described, for instance, in the aforementioned Johnstone et al. Reissue Patent No. 22,566. Thus a methylated methylol melamine may be produced by effecting reaction under acidic conditions between a polymethylol melamine and methyl alcohol in the ratio of 1 mol of the former to from 2 to 6 mols of the latter, depending upon the number of methylol groupings in the melamine derivative and the extent of methylation (or etherification) desired. The reaction is stopped before the product becomes hydrophobic, alkali is added in an amount at least sufiicient to neutralize the reaction mass, after which the mass is dehydrated under vacuum. The preferred methylated methylol melamines, more particularly poly- (methoxymethyD- melamines, are miscible with water in all proportions at room temperature and are stable on storage at 120 F. for at least two weeks.

A more detailed description of the preparation of a substantially completely water-soluble heatcurable or thermosetting, methylated polymethylol melamine which is especially suitable for use in practicing our invention follows:

One mol of melamine is mixed with 3.3 mols of aqueous 37% formaldehyde previously adjusted to a pH of approximately 8.0, the temperature being raised to 70 C. and maintained at this point until a clear solution is obtained. The solution is then immediately cooled and allowed to set, after which the mass is broken into small pieces and dried by circulating warm air at a temperature not exceeding 55 C. The resulting dried powder is alkylated by admixture with twice its weight of 95% methanol containing 0.5% of oxalic acid crystals, based on theweight of the methylol melamine. The mixture is heated to 70 C. and held at this temperature for approximately 15 minutes, or until a clear solution is obtained, whereupon it is immediately neutralized by the addition of sufficient sodium hydroxide solution to raise the pH to approximately 9.0. The neutralized reaction mass is then evaporated to solids under reduced pressure so that the temperature does not rise above 50 C.

The melamine fluosilicates and fluoborates may be prepared in various ways, for example, by allowing melamine and the acid corresponding to the salt desired to react. Thus, aqueous fluosilicic acid or fiuoboric acid may be added to an aqueous solution or dispersion of melamine in water. If the normal salts are desired, we employ one-half mol of fiuosilicic acid or one-third mol of fiuoboric acid per mol of melamine. If the acid salt of fiuosilicic acid is desired, we use one mol of fiuosilicic acid per mol of melamine. If the monohydrogen dimelamine fiuoborate is desired, we employ two-thirds mol of fiuoboric acid per mol of melamine, and if the melamine dihydrogen fiuoborate is wanted we use one mol of fiuoboric acid per mol of melamine. Mixtures of normal and acid salts obtained by reaction oi melamine and fiuosilicic or fluoboric acid may be produced and used in practicing our invention,

if desired. It is not necessary that the salts formed by reaction between the melamine and the acid be isolated, and the solutions or dispersions thereof may be used if one wishes to do so. On the other hand, the anhydrous melamine fiuosilicate or fiuoborate can be isolated if desired by evaporation of the water from the reaction mass or by precipitation of the salt with an organic solvent in which it is insoluble.

In preparing the textile-finishing compositions of our invention the melamine fiuosilicate or fiuoborate or mixture thereof, either in isolated state or as an aqueous solution or dispersion, is added to the aqueous solution or dispersion of the alkylated methylol melamine in an amount such that the proportions of the two ingredients are within the range hereinbefore mentioned. After producing a homogeneous composition, as by thorough agitation, the resuiting aqueous composition may be diluted with water, as desired or as may be required, in order to obtain a finishing composition having the concentration of solids desired for textile application. For example the concentration of solids in the aqueous composition may be, for instance, from 2 to 40 or 45% (about 2 to about 40 or 45%) by weight of the composition depending, for

' example, upon the method of expression or squeezing of the wet, impregnated textile. Ordinarily, however, the alkylated methylol melamine and melamine salt together constitute from about 4 or 5% to about 30 or 35% by weight of the finishing composition.

In addition to imparting valuable insecticidal properties (e. g., resistance to attack by carpet beetle larvae) to the finished, treated wool-containing textile material, the melamine fiuosilicates and fiuoborates used in practicing our invention also have the unique property of functioning as catalysts for accelerating the curing or conversion of the alkylated methylol melamine to a cured, water-insoluble condition or state. In order to speed up the curing of the alkylated methylol melamine or to decrease the heating time, other catalysts may be added, if desired, to the textile-finishing composition, e. g.,

' oxalic acid, acetic acid, phosphoric acid, diammonium hydrogen phosphate, diammonium ethyl phosphate, diammonium phthalate, ammonium chloride, ammonium silicofiuoride, zinc chloride, and others which are known to be catalysts for curing modified or unmodified melamine-formaldehyde reaction products including the alkylated-methylol melamines. The amount of catalyst may be varied as desired or as conditions may require, but ordinarily the catalyst is employed in an amount corresponding to form 0.5

to 5% by weight of the alkylated methylol melamine. If the melamine fiuosilicate or fiuoborate is desired to function both as a catalyst and as an insecticide, the amount thereof which is present in the finishing composition may be increased so that there is available a sufiicient quantity of the salt to provide both the desired catalytic and insecticidal effects. In other words, from 0.5 to 5%, by weight of the alkylated methylol melamine, of the melamine salt, in addition to the amounts previously mentioned, may be employed for accelerating the curing of the alkylated methylol melamine.

The textile-finishing composition comprising an oqueous solution of alkylated methylol melamine, e. g., water-soluble methylated methylol melamine, and at least one compound of the class consisting of melamine fiuosilicates and melamine fiuoborates should contain the melamine salt in'a weight ratio of from 0.05 to 1 part, more particularly from 0.05 to about 0.6 or about 0.7 part, of the said salt for each part of the alkylated methylol melamine in order to obtain satisfactory results. If less than 0.05 (about 0.05) part of the melamine salt be employed for each part of the alkylated methylol melamine, the finished textile will not be rendered adequately resistant to attack by various insects and insect larvae including carpet beetle larvae. 0n the other hand, if substantially more than 1 part, say, 2 or 3 or more parts, of the melamine salt be used for each part of the alkylated methylol melamine, a considerable amount of the melamine salt is washed out of the finished textile on repeated launderings and is economically undesirable. Good results are obtained when the alkylated methylol melamine constitutes, by weight, a major or larger proportion and the melamine salt a minor or lesser proportion of the mixture of the two, e. g., from, by weight, to 95% (about 55 to about 95%) of the former to from 45 to 5% (about 45 to about 5%) of the latter.

Other adjuvants may be added to the textilefinishing composition as desired or as conditions may require. agents, e. g., hexamethylene tetramine, or other agents which will bring the composition to the particular pH desired for application of the composition to the textile material to be treated. The composition may be adjusted so that it is either alkaline, neutral or acid as it is applied to the woolen fabric or other wool-containing textile. The textile-finishing composition also may contain pigments, dyes, softeners, penetrating agents or other insecticides, bactericides or fungicides, or other adjuvants employed in textile-finishing materials including surface-active .agents, e. g., dioctyl sodium sulfo succinate, isoprcpylnaphthalene sodium sulfonate, etc.

When the woolen fabric or other wool-containing textile material is impregnated with 100%, by weightof the dry textile, of the textile finishing composition, the impregnated textile will contain, after drying and curing of the alkylated methylol melamine, approximately the same percentage of cured resin admixed or combined with the melamine salt as the percentage of alkylated methylol melamine and melamine salt which is present in the textile-finishing com- 1 position. i

The alkylated methylol melamine and melamine fiuosilicate or fiuoborate or mixture thereof may be applied to the wool-containing textile material in various ways. For example, if the alkylated methylol melamine and melamine salt are applied in the form of an aqueous solution or dispersion containing the same, the dry or substantially dry textile to be treated may be immersed in the aqueous composition and then passed through pressure rolls, mangles or centrifugal extractors to secure uniform impregnation and a controlled removal of the excess material. The fabric or other textile, however, may be impregnated by other methods, e. g., by spraying.

The pick-up of the aqueous finishing composition by the wool-containing textile material should be adjusted so that the finished textile contains from 2 to 25% (about 2 to about 25%), more particularly from 4, 5 or 6 up to 15, 20 or 25%, by weight of the dry textile, of the cured alkylated methylol melamine admixed or other- These may include buffering" wise combined with the aforementioned melamine salt or salts. The proportions of these ingredients in the finished textile will be of the same general order as the proportions of the alkylated methylol melamine and melamine salt in the textile-finishing composition as applied to the textile. The amount of the aqueous finishing composition picked up by the textile, that is, the so-called "wet pick-up, may be varied as desired or as conditions may require and may range, for example, from about 40 or 50 up to about 150% or more by weight of the dry textile depending, for example, upon the particular textile treated, method and conditions of treatment, concentration of solids in the impregnating bath, amount of solids and properties desired in the finished textile, etc.

The wet, impregnated woolen, fabric or other wool-containing textile material is then dried and cured. The drying and curing temperatures may be varied considerably, but ordinarily temperatures within the range of 160 F. (about 160 F.) to 400 F. (about 400 F.) are employed. The impregnated textile may be dried at a relatively low temperature of the order of 160 F? to 212 F. to remove all or most of the water, after which the dried material is heated at a temperature within the range of 250 F. to 400 F. (about 250 F. to about 400 F.) to convert or cure the curable alkylated methylol melamine admixed with the aforementioned melamine salt or salts to a substantially water-insoluble condition. As a result of this heat-curing of the alkylated methylol melamine in the presence of the melamine fiuosilicate or fluoborate or mixture thereof, the melamine salt becomes fixed by the cured methylol melamine derivative and may chemically react with the methyiol melamine derivative or with any free formaldehyde therein, thereby forming in situ a resinous complex which functions to impart both shrinkage resistance and resistance to attack by various insects and insect larvae, specifically carpet beetle larvae, to the treated textile. That such a reaction actually does take place is supported by other known facts, for instance the outstanding washfastness of the treated textile and the fact that it is known that a reaction can take place between melamine or a melamine salt and a methylol melamine.

The drying and curing operation is flexible and may be varied to suit the available equipment. Continuous methods are preferred. However, drying and curing also may be effected by framing the impregnated fabric to width, as on a pin tenter, drying the framed fabric, batching it upon a shell and then allowing it to stand hot for a period sufficient to convert the solid impregnant in situ to a water-insoluble state. In some cases drying and curing for 2 or 3 hours at 200 F. may be required. Heating the dried fabric at higher temperatures ranging from a few seconds to a few minutes at higher temperatures of the order of 250 F. to 400 F. may be employed, the shorter periods being used at the higher temperatures.

After the woolen fabric or other wool-containing textile material has been treated as above described, it may be given a mild soaping treatment to render it softer and more pliable. It then may be given the usual finishing treatments such as decatizing, brushing, shearing, pressing, etc. Our process may be applied to colored goods as well as to whites without appreciably affecting Example 1 Forty-five parts of aqueous methylated methylol melamine containing about 80% of solids was diluted with 100 parts of water, to which was then added 50 parts of an aqueous solution containing about 2.3% thereof of diammonium hydrogen phosphate and about 0.3% of hexamethylene tetramine. Three and five-tenths parts of a melamine fiuosilicate was dissolved 4 in 151 parts of water, and the resulting aqueous solution of the melamine salt was added to the above-described solution of methylated methylol melamine, diammonlum hydrogen phosphate and hexamethylene tetramine.

The melamine fiuosilicate was prepared as follows: One-half mol (63 grams) of melamine was dissolved in two liters of hot (65 C.) water containing 45 milliliters of 36% hydrochloric acid. In a separate vessel 94 grams of sodium fluosilicate (NarSiFs) was dissolved in two liters of water containing 70 milliliters of 36% hydro-' chloric acid, It was necessary to boil this solution in order to dissolve the sodium fluosllicate. The resulting clear solution was added slowly to the solution of melamine hydrochloride, yielding a line, white precipitate of melamine fiuosilicate which was filtered oil, dried and used as described above.

A piece of woolen flannel goods (35 parts) was immersed in the textile-finishing composition prepared as above described, and then squeezed through a wringer so that the fabric retained about by weight of the dry fabric, of the impregnating composition. The impregnated fabric was dried first at F. and then heated to approximately 300 F. for 10 minutes to cure the methylated methylol melamine to a waterinsoiuble condition.

A portion of the treated woolen material was then washed five times by a standard laundering procedure as outlined on pages 225-226 of the 1943 Year Book of the American Association of Textile Chemists and Colorists. There was no appreciable shrinkage in either the warp or the filling of the treated piece, as compared with a shrinkage of 35% in the warp and 51% in the filling for the untreated woolen material when washed five times by the same laundering procedure.

The treated pieces, both washed and unwashed, were then evaluated for insecticidal and mothprooiing properties by exposure to the action of black carpet beetle larvae for two weeks. At the end of this period there were no holes in the unwashed fabric and no evidence of the nap having been eaten. The washed sample likewise showed no holes at the end of the test period. A check test on an untreated piece of the same woolen fabric showed three large and four small holes at the end of the two weeks period.

Example 2 Same as Example 1 with the exception that 7 parts of the same melamine fluosilicate was used instead of 3.5 parts. After 5 launderings the treated sample showed 1.3% shrinkage in the warp and 8.6% in the filling. After the moth test had been completed, the treated pieces, both washed and unwashed, showed no holes while the untreated piece showed three large and four small holes.

Example 3 Same as Example 1 with the exception that 3.5 parts of a melamine fluoborate was used instead of 3.5 parts of melamine fiuosilicate.

The melamine fiuoborate was prepared as follows: One-half mol (63 grams) of melamine was dissolved in 2 /2 liters of boiling water, and to the resulting solution was added 160 grams of a 42% aqueous solution of IIBFd. On standing, a precipitate of melamine fiuoborate formed. This salt was filtered off, dried and used as described above.

After five launderings the treated sample showed 1% shrinkage in the warp and in the filling. After the moth test the treated pieces, both washed and unwashed, showed no holes Whereas the untreated piece showed seven holes. As in the case of the treated samples of Examples 1 and 2, the fact that no holes appeared in the washed samples after exposure for two weeks to black carpet beetle larvae shows that the insecticidal properties of the treated goods were retained even after repeated launderings.

Example 4 Same as Example 1 with the exception that 7 parts of the same melamine fluoborate used in Example 3 was employed instead of 3.5 parts of melamine fluosilicate. After five launderings there was no appreciable shrinkage in either the warp or the filling of the treated piece. The unwashed treated sample showed no holes and no indication of the nap having been eaten at the end of the moth test, whereas the untreated piece showed seven holes.

The present invention provides a rapid, economical and convenient means of rendering a wool-containing textile material resistant to shrinking and felting and, also, to attack by insects, e. g., the common carpet beetle, the furniture carpet beetle, the tapestry moth, the casemaking clothes moth, the webbing clothes moth, and other insects which attack wool-containing and other textiles. The treated textile is resistant to dry cleaning and soaping or other washing, cleaning or laundering operations; that is, the insecticide is so bound, probably by chemical reaction, that it is not easily or readily removed, if at all, when the fabric is washed or otherwise cleaned. Furthermore, the insecticidal action of the melamine fiuosilicate or fluoborate or mixture thereof continues to prevail even though it is homogeneously distributed throughout, or imbedded in, or otherwise combined with, a resin, specifically a cured alkylated methylol melamine, which itself is resistant to laundering and is capable of imparting shrinkage resistance to the wool-containing textile material.

In a manner similar to that described hereinbefore with particular reference to the use of melamine fluosilicate 'or melamine fluoborate or mixtures thereof in combination with an alkylated methylol melamine, other salts (addition salts) obtained by reaction of melamine or other saltforming aminotriazine and an inorganic acid having a fluorine-containing anion may be employed. Examples of such salts are melamine fluoaluminates, melamine fiuotitanates and the like. Examples of aminotriazines other than melamine that may be used in forming such salts with fluosilicic acid, fluoboric acid or other inorganic acid having a fluorine-containing anion are, for instance, monomethyl melamine (Z-N-methylamino-4,6-diamino-l,3,5-triazine), monophenyl melamine, formoguanamine, stearoguananiine, lauroguanamine, and others described, for example, in Thurston Patent No. 2,309,679. Also, instead of applying the melamine or other aminotriazine salt as such to the textile material, we may first form an aldehyde-reaction product thereof, e. g., a methylol derivative of the melamine salt, and then impregnate the wool-containing textile material with such an aldehydereaction product in combination with an alkylated methylol melamine in the same manner as described hereinbefore with reference to the use of a melamine salt.

We claim:

l. The method of rendering a wool-containing textile material resistant to shrinking and to attack by carpet beetle larvae which comprises impregnating the said textile material with a combination of (1) an alkylated methylol melamine which is at least partlysoluble in water and (2) at least one compound of the class consisting of melamine fluosilicates and melamine fluoborates, the components of (l) and (2) being applied to the said textile material in a weight ratio of from 0.05 to 1 part of the latter for each part of the former, and curing in situ the alkylated methylol melamine of (l) in intimate contact with the compound of (2) to a substantially water-insoluble state, the total amount of the components of (l) and (2) which is applied to the said textile material being such that the finished textile contains from 2 to 25%, by weight of the dry textile, of an impregnant comprising cured alkylated methylol melamine in combination with 'the compound of (2),.

2. A method as in claim 1 wherein the compound of (1) is a water-soluble methylated methylol melamine.

3. A method as in claim 1 wherein the compound of (2) is a melamine fluosilicate.

4. A method as in claim 1 wherein the compound of (2) i: a melamine fluoborate.

5. The method of both shrinkproofing and mothproofing a woolen fiabric material which comprises impregnating said fabric material with from 4 to 25%, by weight of the dry fabric, of a mixture comprising (1) a water-soluble methylated methylol melamine and (2) at least one compound of the class consisting of melamine fluosilicates and melamine fluoborates, the components of (1) and (2) being present in the said mixture in a weight ratio of from 0.05 to 1 part of the latter for each part of the former, and the said mixture being applied to the said fabric material in the form of a substantially homogeneous aqueous composition containing the same, and thereafter drying the impregnated fabric material and curing the methylated methylol melamine in the presence of the said compound of (2) to a substantially water-insoluble state.

6. The method of rendering a woolen textile material resistant to shrinking and to attack by carpet beetle larvae which comprises impregnating said textile material with from 4 to 25%, by weight of the dry textile, of a mixture comprising (1) a water-soluble methylated methylol melamine and (2) a melamine fluosilicate, the components of (1) and (2) being present in the said Eli said mixture being applied to the said textile amine while intimately associated with the said compound of (2) to a substantially water-insolubie condition.

7. A method as in claim 6 wherein the compound of (2) is a'melamine fiuoborate.

8. A textile-finishing composition comprising a homogeneous association of ingredients comprising 1) an allgvlated methylol melamine which is at least partly soluble in water and (2) at least one compound of the class consisting of melamine fluosilicates and melamine fluoborates in a ratio, by weight, corresponding to from 0.05 to 1 part of the compound of (2) for each part of the alkylated methylol melamine of (1).

9. A composition as in claim 8 wherein the component of (1) is a water-soluble methylated methylol melamine.

10. A composition as in claim 8 wherein the compound of (2) is a melamine fluosilicate.

11. A composition as in claim 8 wherein the compound of (2) is a melamine fluoborate.

12. As a new textile-finishing agent especially adapted for rendering a wool-containing textile material resistant to shrinking and to attack by carpet beetle larvae, an aqueous liquid composition comprisin (1) a water-soluble methylated methylol melamine and (2) at least one compound of the class consisting of melamine fluosilicates and melamine fiuoborates in a ratio, by weight, corresponding to from 0.05 to 0.8 part of the compound of (2) for each part of the methylated methylol melamine of (l).

13. A textile-finishing agent comprising an aqueous composition containing (1) a watersoluble methylated methylol melamine and (2) at least one compound of the class consisting of melamine fiuosilicates and melamine fiuoborates in a ratio, by weight, corresponding to from 0.05 to 0.6 part of the compound of (2) for each part of the methylated methylol melamine of (l), and said ingredients of (1) and (2) together constituting from 2 to 45% by weight of the said composition.

14. A wool-containing textile material which is resistant to shrinking and to attack by carpet beetle larvae and which contains from 2 to 25%, by weight of the dry textile material, of an impregnant comprisin (1) a cured alkylated methylol melamine intimately associated with (2) at least one compound of the class consisting of melamine fluosilicates and melamine fiuoborates, the alkylated methylol melamine before curing being at least partly soluble in water, and the compound of (2) and the uncured alkylated methylol melamine being applied to the said textile material in a weight ratio of from 0.05 to 1 part of the former for each part of the latter.

15. A shrink-resistant, moth-resistant, woolen s2 fabric material which is homogeneously impregnated with from 4 to 25%, by weight of the dry fabric material, of an impregnant comprising (1) a cured methylated methylol melamine in a substantially water-insoluble condition and (2) a melamine fluosilicate, the methylated methylol melamine before curing being water-soluble, and the said melamine iiuosilicate of (2) and the uncured methylated methylol melamine being applied to the said fabric material in a weight ratio of from 0.05 to 1 part of the former for each part of the latter.

16. A shrink-resistant, moth-resistant woolen fabric material which is homogeneously impregnated with from 4 to 25%, by weight of the dry fabric material, of an impregnant comprising (1) a cured methylated methylol melamine in a substantially water-insoluble condition and (2) a melamine fiuoborate, the methylated methylol melamine before curing being water-soluble, and the said melamine fluoborate of (2) and the uncured methylated methylol melamine being applied to the said fabric material in a weight ratio of from 0.05 to 1 part of the former for each part of the latter.

17. The method of rendering woolen textile material resistant to shrinking and to attack by carpet beetle larvae which comprises (1) impregnating the said textile material with an impregnating composition consisting of an aqueous solution of methylated methylol melamine containing a small amount of both diammonium hydrogen phosphate and hexamethylene tetramine, the said phosphate being present in the said solution in a major proportion with respect to the said hexamethylene tetramine, and the said solution also containing melamine fluosilicats in a. Weight ratio of about 1 part thereof to about 10 parts of the said methylated methylol melamine on a net dry basis, (2) squeezing the impregnated textile material so that it retains about by weight of the dry textile, of the REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date Re. 22,566 Johnstone Nov. 21, 1944 1,915,334 Salzberg June 27, 1933 2,075,359 Salzberg Mar. 20, 1937 2,267,871 Martin Dec. 20, 1941 2,318,121 Widmer May 4, 1943 2,368,451 DAlelio Jan. 20, 1945 2,388,143 Harris Oct. 20, 1945 Certificate of Correction Patent No. 2,514,132 July 4, 1950 ROY H. KI ENLE ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 50, for water-soluble read water-insoluble; column 3, line 75,

for tedencies read tendencies; column 5, line 57, for form read from; line 72, for oqueous read aqueous; column 10, line 48, for fiabric read fabric and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 31st day of October, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

8. A TEXTILE-FINISHING COMPOSITION COMPRISING A HOMOGENEOUS ASSOCIATION OF INGREDIENTS COMPRISING (1) AN ALKYLATED METHYLOL MELANMINE WHICH IS AT LEAST PARTLY SOLUBLE IN WATER AND (2) AT LEAST ONE COMPOUND OF THE CLASS CONSISTING OF MELAMINE FLOUSILICATES AND MELAMINE FLUOBORATES IN A RATIO, BY WEIGHT, CORRESPONDING TO FROM 0.05 TO 1 PART OF THE COMPOUND OF (2) FOR EACH PART OF THE ALKYLATED METHYOL MELAMINE OF (1). 